CN106012567A - 一种环保抗菌型tpu合成革及其制备方法 - Google Patents
一种环保抗菌型tpu合成革及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种TPU合成革,所述TPU合成革包括依次贴合的基材层和聚氨酯发泡层;所述基材层为锦纶超细纤维和芳纶纤维的混纺无纺布层;所述聚氨酯发泡层通过将如下第一预聚体和第二预聚体交联得到;所述第一预聚体和第二预聚体交联的交联剂为三羟甲基丙烷,交联过程中,第一预聚体和第二预聚体的质量比为1:1.5~3.5;在所述第一预聚体和第二预聚体交联过程中添加有茶皂素。本发明通过选用特定的聚合单体发生交联,在特定比例下,能够获得力学性能优异的柔软合成革材料,第一预聚体、第二预聚体、交联剂、发泡剂、抗菌剂在特定组成下协同增效获得了优异的力学性能和阻燃性能。
Description
技术领域
本发明涉及材料领域,具体涉及一种环保抗菌型TPU合成革及其制备方法。
背景技术
合成革是一种模拟天然革的组成和结构,并可作为其代用材料的塑料制品,其广泛应用于制作鞋、靴、箱包和球类等制品。目前,市场上使用的合成革通常以经浸渍的无纺布为网状层,微孔聚氨酯层作为粒面层制得,并具有一定的透气性,但是这种合成革的疏水性较差,导致其防水效果不佳,也间接影响了合成革的透气性能。而且,超细纤维合成革类似于天然皮革的三维网络结构,使其具有很好的仿真皮效果,但与天然皮革相比超细纤维合成革的绒毛较短、较少,在绒感和书写效应方面与真皮有明显差距,因此,针对以上缺陷,还有待改进。
TPU压延环保合成革即通过压延生产工艺制得的皮革,攻克压延工艺对TPU材料的限制,可直接通过压延工艺生产100%环保皮革制品。然而并非所有的TPU弹性体都可应用于压延制程,且亦非所有TPU压延级产品都可生产皮革。
热塑性聚氨酯(TPU)不仅具有优良的物理机械性能,如高模量、高强度、高伸长、高弹性、韧性好,还具有低温柔软性好、耐磨、耐油、透气性好等优点,并且可以回收利用二次加工成型。因此,TPU广泛地应用于塑料薄膜、汽车、电线电缆、胶粘剂、医疗、鞋底材料、玩具、服饰、管材、滚轮、航空等行业。
目前,抗菌聚氨酯合成革的主要技术途径是向配方中添加各类抗菌剂,实现抗菌功效。技术较为成熟,具有一定应用价值的抗菌剂主要有无机抗菌剂、人工合成有机抗菌剂、高分子抗菌剂和天然产物抗菌剂。其中天然产物抗菌剂是动植物提取物,主要有超细结构的壳聚糖粉末,甲壳素类及各种植物分泌物等,但这类抗菌剂存在耐热性差、药效持续时间短等缺陷,同时,天然产物抗菌剂还受到自然环境因素影响,难以达到量产规模,商业应用价值较低。有机抗菌剂和高分子抗菌剂主要为各类有机含氮离子化合物,有机硅化合物,有机锡类化合物,氨基酸金属盐类及各类含季铵盐、季膦盐、胍盐基团接枝聚合物等。这类抗菌剂虽然具有杀菌能力强,响应时间短,针对性强等优点,但是也存在着耐热性差,易水解变性,抗菌广谱性差,挥发性大,且有一定毒性等问题,所以限制了其应用。无机抗菌剂主要是各类载银、铜、锌离子的微孔纳米化合物,纳米金属氧化物等。但无机抗菌剂同样存在着杀菌、抑菌响应时间长,容易致使产品变色的问题。
本领域需要开发一种环保抗菌型型TPU合成革及其制备方法。
发明内容
本发明的目的之一在于提供一种TPU合成革,所述TPU合成革包括依次贴合的基材层和聚氨酯发泡层;
所述基材层为锦纶超细纤维和芳纶纤维的混纺无纺布层;所述基材层的纤维直径≤5μm;
所述聚氨酯发泡层通过将如下第一预聚体和第二预聚体交联得到:
所述第一预聚体的聚合单体为:聚醚二元醇和异佛二酮二异氰酸酯;
所述第二预聚体的聚合单体为:TDI和ε-己内酯;
所述第一预聚体和第二预聚体交联的交联剂为三羟甲基丙烷,交联过程中,第一预聚体和第二预聚体的质量比为1:1.5~3.5;
在所述第一预聚体和第二预聚体交联过程中添加有茶皂素。
本发明选用茶皂素作为抗菌剂,能够与聚氨酯相互交联,获得机械性能优异的具有抗菌性能的聚氨酯。
优选地,在所述第一预聚体和第二预聚体交联过程中添加有阴离子表面活性剂和非离子表面活性剂。
优选地,所述阴离子表面活性剂的含量为聚醚二元醇质量的1~2wt%。
优选地,所述非离子表面活性剂的含量为聚醚二元醇质量的0.3~0.8wt%。
优选地,所述阴离子表面活性剂为月桂酸钠。
优选地,所述非离子表面活性剂为烷基糖苷。
优选地,所述茶皂素的添加量为聚醚二元醇质量的3~5wt%。
优选地,所述第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 30~70
聚醚二元醇 10~20
扩链剂 1~5
催化剂 0.05~0.1
溶剂 5~10
4A分子筛 5~8
水 40~80。
优选地,所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 30~70
ε-己内酯 15~35
扩链剂 1~5
催化剂 0.05~0.1
溶剂 5~10
4A分子筛 5~8
水 40~80。
优选地,所述聚醚多元醇的分子量为1200~1500。
优选地,所述扩链剂为小分子扩链剂,优选1,4-丁二醇。
优选地,所述催化剂为辛酸亚锡。
优选地,所述交联剂为三羟甲基丙烷。
优选地,所述交联过程使用中和剂终止反应,所述中和剂为三乙胺。
优选地,在所述第一预聚体和第二预聚体交联过程中,还添加有增塑剂;
优选地,所述增塑剂为DEHP。
本发明目的之二是提供一种如目的之一所述TPU合成革的制备方法,所述方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至60~70℃,进行反应0.5~1h;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至50~60℃,进行反应0.5~1h;
(3)交联
将第一预聚体和第二预聚体混合,加入阴离子表面活性剂、非离子表面活性剂、茶皂素和交联剂在70~75℃反应1~2h,之后加入增塑剂、中和剂中和至pH值为7。
与现有技术相比,本发明具有以下有益效果:
本发明通过选用特定的聚合单体发生交联,在特定比例下,能够获得力学性能优异的柔软合成革材料,第一预聚体、第二预聚体、交联剂、发泡剂、抗菌剂在特定组成下协同增效获得了优异的力学性能和阻燃性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至65℃,进行反应0.8h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 40
聚醚二元醇 15
扩链剂 3
催化剂 0.07
溶剂 8
4A分子筛 6
水 60;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至55℃,进行反应0.7h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 40
ε-己内酯 20
扩链剂 3
催化剂 0.08
溶剂 7
4A分子筛 6
水 60;
(3)交联
将第一预聚体和第二预聚体按质量比为1:2混合,加入月桂酸钠(聚醚二元醇的1.5wt%)、烷基糖苷(聚醚多元醇的0.6wt%)、茶皂素(聚醚多元醇的4wt%)和三羟甲基丙烷(聚醚二元醇的4wt%)在73℃反应1.5h,之后加入增塑剂、三乙胺中和至pH值为7。
实施例2
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至60℃,进行反应1h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 30
聚醚二元醇 10
扩链剂 1
催化剂 0.05
溶剂 5
4A分子筛 5
水 40;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至60℃,进行反应0.5h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 70
ε-己内酯 35
扩链剂 5
催化剂 0.1
溶剂 10
4A分子筛 8
水 80;
(3)交联
将第一预聚体和第二预聚体按质量比为1:1.5混合,加入月桂酸钠(聚醚二元醇的1wt%)、烷基糖苷(聚醚多元醇的0.8wt%)、茶皂素(聚醚多元醇的3wt%)和三羟甲基丙烷(聚醚二元醇的5wt%)在70℃反应2h,之后加入增塑剂、三乙胺中和至pH值为7。
实施例3
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至70℃,进行反应0.5h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 70
聚醚二元醇 20
扩链剂 5
催化剂 0.1
溶剂 10
4A分子筛 8
水 80;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至60℃,进行反应0.5h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 30
ε-己内酯 15
扩链剂 1
催化剂 0.05
溶剂 5
4A分子筛 5
水 40;
(3)交联
将第一预聚体和第二预聚体按质量比为1:3.5混合,加入月桂酸钠(聚醚二元醇的2wt%)、烷基糖苷(聚醚多元醇的0.3wt%)、茶皂素(聚醚多元醇的5wt%)和三羟甲基丙烷(聚醚二元醇的3wt%)在75℃反应1h,之后加入增塑剂、三乙胺中和至pH值为7。
对比例1
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至65℃,进行反应0.8h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 40
聚醚二元醇 15
扩链剂 3
催化剂 0.07
溶剂 8
4A分子筛 6
水 60;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至55℃,进行反应0.7h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 40
ε-己内酯 20
扩链剂 3
催化剂 0.08
溶剂 7
4A分子筛 6
水 60;
(3)交联
将第一预聚体和第二预聚体按质量比为1:4混合,加入月桂酸钠(聚醚二元醇的1.5wt%)、烷基糖苷(聚醚多元醇的0.6wt%)、茶皂素(聚醚多元醇的4wt%)和三羟甲基丙烷(聚醚二元醇的4wt%)在73℃反应1.5h,之后加入增塑剂、三乙胺中和至pH值为7。
对比例2
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至65℃,进行反应0.8h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 40
聚醚二元醇 15
扩链剂 3
催化剂 0.07
溶剂 8
4A分子筛 6
水 60;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至55℃,进行反应0.7h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 40
ε-己内酯 20
扩链剂 3
催化剂 0.08
溶剂 7
4A分子筛 6
水 60;
(3)交联
将第一预聚体和第二预聚体按质量比为1:1混合,加入月桂酸钠(聚醚二元醇的1.5wt%)、烷基糖苷(聚醚多元醇的0.6wt%)、茶皂素(聚醚多元醇的4wt%)和三羟甲基丙烷(聚醚二元醇的4wt%)在73℃反应1.5h,之后加入增塑剂、三乙胺中和至pH值为7。
对比例3
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至65℃,进行反应0.8h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 40
聚醚二元醇 15
扩链剂 3
催化剂 0.07
溶剂 8
4A分子筛 6
水 60;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至55℃,进行反应0.7h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 40
ε-己内酯 20
扩链剂 3
催化剂 0.08
溶剂 7
4A分子筛 6
水 60;
(3)交联
将第一预聚体和第二预聚体按质量比为1:2混合,加入茶皂素(聚醚多元醇的4wt%)和三羟甲基丙烷(聚醚二元醇的4wt%)在73℃反应1.5h,之后加入增塑剂、三乙胺中和至pH值为7。
对比例4
一种TPU合成革,方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至65℃,进行反应0.8h;
第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 40
聚醚二元醇 15
扩链剂 3
催化剂 0.07
溶剂 8
4A分子筛 6
水 60;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至55℃,进行反应0.7h;
所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 40
ε-己内酯 20
扩链剂 3
催化剂 0.08
溶剂 7
4A分子筛 6
水 60;
(3)交联
将第一预聚体和第二预聚体按质量比为1:2混合,加入月桂酸钠(聚醚二元醇的1.5wt%)、烷基糖苷(聚醚多元醇的0.6wt%)、纳米银(聚醚多元醇的4wt%)和三羟甲基丙烷(聚醚二元醇的4wt%)在73℃反应1.5h,之后加入增塑剂、三乙胺中和至pH值为7。
性能测试
对实施例和对比例得到的复合材料进行邵氏A硬度测试(GB/T531-1999),拉伸强度测试(GB/T528-1998),延伸率(断裂伸长率GB/T528-1998),密度(GB/T6343-1995),冲击回弹(GB/T1681-1991),抗菌性(GB/Y24346-2009平面培养法)测试,结果见表1:
表1实施例和对比例得到的复合材料的性能测试结果
本发明通过选用特定的聚合单体发生交联,在特定比例下,能够获得力学性能优异的柔软合成革材料,第一预聚体、第二预聚体、交联剂、发泡剂、抗菌剂在特定组成下协同增效获得了优异的力学性能和阻燃性能。
申请人声明,本发明通过上述实施例来说明本发明的工艺方法,但本发明并不局限于上述工艺步骤,即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (9)
1.一种TPU合成革,其特征在于,所述TPU合成革包括依次贴合的基材层和聚氨酯发泡层;
所述基材层为锦纶超细纤维和芳纶纤维的混纺无纺布层;所述基材层的纤维直径≤5μm;
所述聚氨酯发泡层通过将如下第一预聚体和第二预聚体交联得到:
所述第一预聚体的聚合单体为:聚醚二元醇和异佛二酮二异氰酸酯;
所述第二预聚体的聚合单体为:TDI和ε-己内酯;
所述第一预聚体和第二预聚体交联的交联剂为三羟甲基丙烷,交联过程中,第一预聚体和第二预聚体的质量比为1:1.5~3.5;
在所述第一预聚体和第二预聚体交联过程中添加有茶皂素。
2.如权利要求1所述的TPU合成革,其特征在于,在所述第一预聚体和第二预聚体交联过程中添加有阴离子表面活性剂和非离子表面活性剂;
优选地,所述阴离子表面活性剂的含量为聚醚二元醇质量的1~2wt%;
优选地,所述非离子表面活性剂的含量为聚醚二元醇质量的0.3~0.8wt%;
优选地,所述阴离子表面活性剂为月桂酸钠;
优选地,所述非离子表面活性剂为烷基糖苷。
3.如权利要求2所述的TPU合成革,其特征在于,所述茶皂素的添加量为聚醚二元醇质量的3~5wt%。
4.如权利要求1~3之一所述的TPU合成革,其特征在于,所述第一预聚体的制备原料按重量份数包括如下组分:
异佛二酮二异氰酸酯 30~70
聚醚二元醇 10~20
扩链剂 1~5
催化剂 0.05~0.1
溶剂 5~10
4A分子筛 5~8
水 40~80。
5.如权利要求1~4之一所述的TPU合成革,其特征在于,所述第二预聚体的制备原料按重量份数包括如下组分:
MDI 30~70
ε-己内酯 15~35
扩链剂 1~5
催化剂 0.05~0.1
溶剂 5~10
4A分子筛 5~8
水 40~80。
6.如权利要求1~5之一所述TPU合成革,其特征在于,所述聚醚多元醇的分子量为1200~1500;
优选地,所述扩链剂为小分子扩链剂,优选1,4-丁二醇;
优选地,所述催化剂为辛酸亚锡。
7.如权利要求1~6之一所述TPU合成革,其特征在于,所述交联剂为三羟甲基丙烷;
优选地,所述交联剂的添加量为聚醚多元醇的3~5wt%;
优选地,所述交联过程使用中和剂终止反应,所述中和剂为三乙胺。
8.如权利要求1~7之一所述TPU合成革,其特征在于,在所述第一预聚体和第二预聚体交联过程中,还添加有增塑剂;
优选地,所述增塑剂为DEHP。
9.一种如权利要求1~8之一所述TPU合成革的制备方法,其特征在于,所述方法包括如下步骤:
(1)制备第一预聚体:
将第一预聚体的原料按配方比混合,升温至60~70℃,进行反应0.5~1h;
(2)制备第二预聚体:
将第一预聚体的原料按配方比混合,升温至50~60℃,进行反应0.5~1h;
(3)交联
将第一预聚体和第二预聚体混合,加入阴离子表面活性剂、非离子表面活性剂、茶皂素和交联剂在70~75℃反应1~2h,之后加入增塑剂、中和剂中和至pH值为7。
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CN111764179A (zh) * | 2020-06-01 | 2020-10-13 | 广西鑫深科技有限公司 | 环保抗菌人造革 |
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